Averaging, polydisperse

The inlet monomer concentration was varied sinusoidally to determine the effect of these changes on Dp, the time-averaged polydispersity, when compared with the steady-state case. For the unsteady state CSTR, the pseudo steady-state assumption for active centres was used to simplify computations. In both of the mechanisms considered, D increases with respect to the steady-state value (for constant conversion and number average chain length y ) as the frequency of the oscillation in the monomer feed concentration is decreased. The maximum deviation in D thus occurs as lo 0. However, it was predicted that the value of D could only be increased by 10-325S with respect to the steady state depending on reaction mechanism and the amplitude of the oscillating feed. Laurence and Vasudevan (12) considered a reaction with combination termination and no chain transfer. 

Figure C2.17.4. Transmission electron micrograph of a field of Zr02 (tetragonal) nanocrystals. Lower-resolution electron microscopy is useful for characterizing tire size distribution of a collection of nanocrystals. This image is an example of a typical particle field used for sizing puriDoses. Here, tire nanocrystalline zirconia has an average diameter of 3.6 nm witli a polydispersity of only 5% 1801.

Hven fractionated polymer samples are generally polydisperse, which means that the molecular weight determined from intrinsic viscosity experiments is an average value. The average obtained is the viscosity average as defined by Eqs. (1.20) and (2.40) as seen by the following argument ... 

For polydisperse systems the value of M obtained from the values of s° and D°-or, better yet, the value of the s/D ratio extrapolated to c = 0-is an average value. Different kinds of average are obtained, depending on the method used to define the average location of the boundary. The weight average is the type obtained in the usual analysis. 

Polydispersity obscures the nature of the average obtained, although the possibility of extracting more than one kind of average from the same data under optimum conditions partially offsets this. 

The diametei of average mass and surface area are quantities that involve the size raised to a power, sometimes referred to as the moment, which is descriptive of the fact that the surface area is proportional to the square of the diameter, and the mass or volume of a particle is proportional to the cube of its diameter. These averages represent means as calculated from the different powers of the diameter and mathematically converted back to units of diameter by taking the root of the moment. It is not unusual for a polydispersed particle population to exhibit a diameter of average mass as being one or two orders of magnitude larger than the arithmetic mean of the diameters. In any size distribution, the relation ia equation 4 always holds. 

Natural latex is polydisperse (size of individual particles may vary from 0.01 to 5 p.m). Flowever, synthetic latex has a relatively narrow particle size, and therefore the viscosity at a given rubber content is higher in synthetic rubber (polyisoprene) solutions. The average molecular weight is typically about I million g/mol, although it depends on the gel content. 

In order to develop integral equations for the correlation functions, we consider the system composed of N polydisperse spheres. The average density of particles with diameter <7, is given by... 

The changes in the average chain length of a solution of semi-flexible selfassembling chains confined between two hard repulsive walls as the width of the sht T> is varied, have been studied [61] using two different Monte Carlo models for fast equihbration of the system, that of a shthering snake and of the independent monomer states. A polydisperse system of chain molecules in conditions of equilibrium polymerization, confined in a gap which is either closed (with fixed total density) or open and in contact with an external reservoir, has been considered. 

Average values dp = 32,000 [glucose units], dp = 900 [glucose units], and the polydispersity of dp, dp = 36 show a broad distribution with the interesting fact that components exceeding dp 3000 represent approximately 3-5% of molar concentration only, whereas mass contribution of these glucans is approximately 60%. 

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